Selective C–H amination of electronically diverse (hetero)arene substrates is reported using an electrochemical strategy. Two convergent mechanistic pathways enable the tolerance of both electron-rich and electron-deficient (hetero)arenes. When electron-deficient substrates are used the process proceeds through electrophilic N-radical dicationic intermediates, following amine oxidation, whereas electron-rich substrates undergo arene oxidation.
- Griffin Stewart
- Eva Maria Alvarez
- Christian A. Malapit